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PubMed1999

Physical properties of solid molecular dispersions of indomethacin with poly(vinylpyrrolidone) and poly(vinylpyrrolidone-co-vinyl-acetate) in relation to indomethacin crystallization.

PURPOSE: To measure solid-state features of amorphous molecular dispersions of indomethacin and various molecular weight grades of poly(vinylpyrrolidone), PVP, and poly(vinylpyrrolidone-co-vinylacetate), PVP/VA, in relation to isothermal crystallization of indomethacin at 30 degrees C. METHODS: The glass transition temperatures (Tg) of molecular dispersions were measured using differential scanning calorimetry (DSC). FT-IR spectroscopy was used to investigate possible differences in interactions between indomethacin and polymer in the various dispersions. The enthalpy relaxation of 5%w/w and 30%w/w polymer dispersions was determined following various aging times. Quantitative isothermal crystallization studies were carried out with pure indomethacin and 5%w/w polymers in drug as physical mixtures and molecular dispersions. RESULTS: All coprecipitated mixtures exhibited a single glass transition temperature. All polymers interacted with indomethacin in the solid state through hydrogen bonding and in the process eliminated the hydrogen bonding associated with the carboxylic acid dimers of indomethacin. Molecular mobility at 16.5 degrees C below Tg was reduced relative to indomethacin alone, at the 5%w/w and 30%w/w polymer level. No crystallization of indomethacin at 30 degrees C was observed in any of the 5%w/w polymer molecular dispersions over a period of 20 weeks. Indomethacin alone and in physical mixtures with various polymers completely crystallized to the y form at this level within 2 weeks. CONCLUSIONS: The major basis for crystal inhibition of indomethacin at 30 degrees C at the 5%w/w polymer level in molecular dispersions is not related to polymer molecular weight and to the glass transition temperature, and is more likely related to the ability to hydrogen bond with indomethacin and to inhibit the formation of carboxylic acid dimers that are required for nucleation and growth to the gamma crystal form of indomethacin.

Calorimetry, Differential Scanning↗

PubMed2002

Folding thermodynamics of model four-strand antiparallel beta-sheet proteins.

The thermodynamic properties for three different types of off-lattice four-strand antiparallel beta-strand protein models interacting via a hybrid Go-type potential have been investigated. Discontinuous molecular dynamic simulations have been performed for different sizes of the bias gap g, an artificial measure of a model protein's preference for its native state. The thermodynamic transition temperatures are obtained by calculating the squared radius of gyration R(g)(2), the root-mean-squared pair separation fluctuation Delta(B), the specific heat C(v), the internal energy of the system E, and the Lindemann disorder parameter Delta(L). Despite these models' simplicity, they exhibit a complex set of protein transitions, consistent with those observed in experimental studies on real proteins. Starting from high temperature, these transitions include a collapse transition, a disordered-to-ordered globule transition, a folding transition, and a liquid-to-solid transition. The high temperature transitions, i.e., the collapse transition and the disordered-to-ordered globule transition, exist for all three beta-strand proteins, although the native-state geometry of the three model proteins is different. However the low temperature transitions, i.e., the folding transition and the liquid-to-solid transition, strongly depend on the native-state geometry of the model proteins and the size of the bias gap.

Biophysical Phenomena↗

PubMed2000

Low concentration of DMSO stabilizes the bilayer gel phase rather than the interdigitated gel phase in dihexadecylphosphatidylcholine membrane.

We have investigated effects of dimethylsulfoxide (DMSO) on the phase stability of multilamellar vesicles of the ether-linked 1,2-dihexadecyl-sn-glycero-3-phosphatidylcholine (DHPC-MLV), which is known to be in the interdigitated gel (LbetaI) phase in excess water at 20 degrees C. The results of X-ray diffraction experiments indicate that the DHPC membrane was in the Lbeta, phase at X> or =0.12 (X=mole fraction of DMSO in DMSO/water mixture). The result of differential scanning calorimetry indicate that the gel to liquid-crystalline phase transition temperature increased, but the LbetaI to Pbeta, phase transition temperature decreased with an increase in DMSO concentration. These results show that DMSO stabilizes the bilayer gel phase rather than the LbetaI phase at its low concentration. The solubility of phosphorylcholine, which is the same structure as the headgroup of DHPC, decreased with an increase in DMSO concentration, indicating that the interaction free energy of the hydrophilic segments of the membrane with solvents increases with an increase in DMSO concentration. On the basis of the thermodynamic analysis, the mechanism of the stabilization of the bilayer gel phase of DHPC-MLV by DMSO is discussed. The decrease in the repulsive interaction between the headgroups of the phospholipid induced by the low concentrations of DMSO in water plays an important role in this stabilization.

Calorimetry, Differential Scanning↗

PubMed2005

Theory of glassy dynamics in conformationally anisotropic polymer systems.

A mode coupling theory for the ideal glass transition temperature, or crossover temperature to highly activated dynamics in the deeply supercooled regime, T(c), has been developed for anisotropic polymer liquids. A generalization of a simplified mode coupling approach at the coarse-grained segment level is employed which utilizes structural and thermodynamic information from the anisotropic polymer reference interaction site model theory. Conformational alignment or/and coil deformation modifies equilibrium properties and constraining interchain forces thereby inducing anisotropic segmental dynamics. For liquid-crystalline polymers a small suppression of T(c) with increasing nematic or discotic orientational order is predicted. The underlying mechanism is reduction of the degree of coil interpenetration and intermolecular repulsive contacts due to segmental alignment. For rubber networks chain deformation results in an enhanced bulk modulus and a modest elevation of T(c) is predicted. The theory can also be qualitatively applied to systems that undergo nonuniversal local deformation and alignment, such as polymer thin films and grafted brush layers, and large elevations or depressions of T(c) are possible. Extension to treat directionally dependent collective barrier formation and activated hopping is possible.

Algorithms↗

PubMed2001

Thermodynamic and transport properties of superconducting Mg10B2.

Transport and thermodynamic properties of a sintered pellet of the newly discovered MgB2 superconductor have been measured to determine the characteristic critical magnetic fields and critical current densities. Both resistive transition and magnetization data give similar values of the upper critical field, Hc2, with magnetization data giving dHc2/dT = 0.44 T/K at the transition temperature of Tc = 40.2 K. Close to the transition temperature, magnetization curves are thermodynamically reversible, but at low temperatures the trapped flux can be on the order of 1 T. The value of dHc/dT at Tc is estimated to be about 12 mT/K, a value similar to classical superconductors like Sn. Hence, the Ginzburg-Landau parameter kappa approximately 26. Estimates of the critical supercurrent density, Jc, using hysteresis loops and the Bean model, give critical current densities on the order of 10(5) A/cm2. Hence the supercurrent coupling through the grain boundaries is comparable to intermetallics like Nb3Sn.

Journal Article↗

PubMed1998

Interaction of alpha-helical peptides with phospholipid membrane: effects of chain length and hydrophobicity of peptides.

To investigate the interaction of amphiphilic alpha-helical peptides with phospholipid membranes, we synthesized Ac-(Leu-Ala-Arg-Leu)3-NHCH3 (4[3]) and three derivatives, in which the chain length and the size of the hydrophobic region of the peptides were different from each other. These peptides formed an alpha-helical structure in the presence of vesicles. In the membrane-perturbation measurement, only 43 showed a strong membrane-perturbation activity below phase-transition temperature (25 degrees C), but above phase-transition temperature (50 degrees C), most peptides showed similar strong activities. On the other hand, in membrane-fusion measurement the long peptides, e.g., Ac-(Leu-Ala-Arg-Leu)3-(Leu-Arg-Ala-Leu)3-NHCH3, had strong activities at low peptide concentrations at 25 degrees C. The present study indicated a parallel relationship did not always exist between membrane fusion and perturbation caused by peptides.

1,2-Dipalmitoylphosphatidylcholine↗

PubMed2004

Determining the critical relative humidity for moisture-induced phase transitions.

A new method to determine the onset relative humidity for a glass transition and crystallization processes in amorphous or partially amorphous materials was developed using dynamic gravimetric vapor sorption (DVS). Water vapor can act as a plasticizing agent in amorphous materials, thus lowering the glass transition temperature below room temperatures. Additional water sorption can lead to a crystallization event below the glass transition temperature. On spray-dried lactose the glass transition RH and crystallization RH values were 30 and 58% at 25 degrees C, respectively. Glass transition and crystallization RH values were also measured at 5, 15, 25, 35, and 45 degrees C on a spray-dried salbutamol sulfate sample. The glass transition RH values for the salbutamol sulfate sample ranged from 64.5% RH (5 degrees C) to 32.8% RH (45 degrees C) while the crystallization RH values ranged from 81.0% RH (5 degrees C) to 50.4% RH (45 degrees C). The results clearly show that the glass transition and crystallization humidity values decrease as the sample temperature increases.

Albuterol↗

PubMed2005

Cooling rate dependence of specific heat in systems out of equilibrium.

The anomaly of specific heat in systems out of equilibrium, especially the measurement procedure dependence of specific heat, is investigated by means of free energy landscape. Introducing measurement procedure which is based on experimental method, we propose a calculation method of specific heat in systems out of equilibrium and find an abrupt change in specific heat between annealed and quenched states. For longer observation time the change in specific heat occurs at lower temperature and becomes sharper. For slower cooling of a system the transition temperature becomes lower. This cooling rate dependence of the transition temperature is consistent with experiments and thus the abrupt change in specific heat can be regarded as the glass transition which is thermally identified.

Journal Article↗

PubMedDate not supplied

Structure and morphology changes during in vitro degradation of electrospun poly(glycolide-co-lactide) nanofiber membrane.

Electrospun poly(glycolide-co-lactide) (PLA10GA90, LA/GA ratio 10/90) biodegradable nanofiber membranes possessed very high surface area to volume ratios and were completely noncrystalline with a relatively lowered glass transition temperature. These characteristics led to very different structure, morphology, and property changes during in vitro degradation, which were examined systematically. A shrinkage study showed that the electrospun crystallizable but amorphous PLA10GA90 membranes exhibited a very small shrinkage percentage when compared with the electrospun membranes of noncrystallizable poly(lactide-co-glycolide) (PLA75GA25, LA/GA 75/25) and poly(d,l-lactide). Although the weight loss of electrospun PLA10GA90 membranes exhibited a similar degradation behavior as cast thin films, detailed studies showed that the structure and morphology changes in electrospun membranes followed different pathways during the hydrolytic degradation. After 1 day of degradation in buffer solution at 37 degrees C, electrospun PLA10GA90 membranes exhibited a sudden increase in crystallinity and glass transition temperature, due to the fast thermally induced crystallization process. The continuous increase in crystallinity and apparent crystal size, as well as the decrease in long period and lamellae thickness, indicated that the thermally induced crystallization was followed by a chain cleavage induced crystallization process. The mass loss rate was accelerated after 6 days of degradation. The increase in glass transition temperature during this period further confirmed that the degradation of PLA10GA90 nanofibers was initiated from the amorphous region within the lamellar superstructures. A mechanism of structure and morphology changes during in vitro degradation of electrospun PLA10GA90 nanofibers is proposed.

Calorimetry, Differential Scanning↗

PubMedDate not supplied

Control by ganglioside GD1a of phospholipase A2 activity through modulation of the lamellar-hexagonal (HII) phase transition.

Ganglioside GD1a has a dual effect on the formation of the HII phase in mixtures of dioleoylphosphatidyl choline (DOPC)-dioleoylphosphatidylethanolamine (DOPE) (1:5). Below 1 mol% ganglioside in the mixture the formation of the HII phase is facilitated as indicated by a decrease of the lamellar-HII phase transition temperature; above 1 mol% the presence of ganglioside GD1a opposes formation of the HII phase and causes an increase of the phase transition temperature; the latter is completely abolished at 3 mol% GD1a or above. The rate of activity of phospholipase A2 against these mixtures showed a temperature variation in coincidence with the establishment of the lamellar-hexagonal II phase transition. In the presence of GD1a at 0.5 and 1 mol% in the mixture, the maximum activity shifted in correspondence with the ganglioside-induced displacement of the lamellar-hexagonal II phase transition. The temperature variation of the enzymatic activity did not show any maximum for pure DOPC of for DOPC-DOPE (1:5) mixtures containing 3 mol% GD1a or above, in which no lamellar-hexagonal II phase transition occurs. The effects of GD1a are probably due to the geometrical features of the ganglioside molecule that allow a composition-dependent compensation of the structural defects required for the formation of the HII phase which are detected by phospholipase A2.

Calorimetry↗

PubMed1982

Hydrophobic membrane interaction of etidocaine, bupivacaine and 2-chloroprocaine. A spin and fluorescent probe study.

It has been suggested that local anesthetics may block sodium conductance through nervous membranes also by hydrophobic interaction, e.g., by expanding the membrane. Decreased anisotropy (fluidization) and depressed phase transition temperatures have been shown by relatively high local anesthetic concentrations. We studied the dose dependence of the effect of three clinically used local anesthetics, with different lipid solubility, on lipid fluidity parameters of four different model membranes. With stearic acid spin labels in dipalmitoyl lecithin vesicles etidocaine (1-5 mM) had the clearest fluidizing effect followed by bupivacaine (5 mM); 2-chloroprocaine was without effect on lipid fluidity. In synaptic plasma membranes a fluidizing effect near the hydrophilic part of the lipid bilayer was similar with etidocaine and bupivacaine (5-10 mM); 2-chloroprocaine had no effect. Bupivacaine at 125 and 250 muM had a small ordering effect, which was not seen at a more hydrophobic site of the membrane. Etidocaine had the strongest fluidizing effect at the latter site of the synaptic plasma membranes. In erythrocyte ghost membranes, probed by stearic acid spin labels near the hydrophilic end, none of local anesthetics affected fluidity at 24 degrees C, while at 37 degrees C etidocaine (1-5 mM) and bupivacaine (5 mM) had a fluidizing effect. Dimyristoyl lecithin vesicles were probed by cis- and trans-parinaric acid. Etidocaine and bupivacaine (5-10 mM) clearly depressed the phase transition temperature evaluated from fluorescence intensity scans. The effect was most marked with bupivacaine (1-10 mM) when cis-parinaric acid was used. While isolated mammalian nerves are blocked by local anesthetic concentrations below 100 muM, this study shows that the clinically used local anesthetics increase fluidity and depress phase transition temperature only at 10-100 times higher concentrations at physiological pH. This kind of hydrophobic membrane interaction may not be important for the nerve blocking effect.

Anesthetics, Local↗

PubMed1999

Physical-property comparison of a chairside- or laboratory-polymerized permanent soft-liner during 1 year.

PURPOSE: This investigation examined the influence of polymerization mode and water storage duration on the Shore A hardness, water sorption, resin solubility, and glass transition temperature of Permasoft, a commercial soft denture liner that is polymerized either chairside or in the laboratory. MATERIALS AND METHODS: Specimen disks (31-mm diameter x 10 mm thick) and bars (44 x 8.5 x 1.2 mm) were polymerized following manufacturer's recommendations. The chairside polymerization process was simulated by pouring the mixed components into a mold and processing at 70 degrees C for 15 minutes under 2-psi pressure. Laboratory-polymerized specimens of the same dimensions were fabricated by processing under 500-psi pressure at 100 degrees C for 45 minutes. Specimens were stored in distilled water at 37 degrees C for 1, 7, and 30 days, and 6 and 12 months. Specimens were tested for Shore A hardness, water sorption, resin solubility, and glass transition temperature after the prescribed interval. To determine the effects of polymerization mode and storage time on material properties, a repeated-measures ANOVA (hardness data) and a two-way ANOVA (sorption and solubility data) with appropriate post-hoc tests were used. RESULTS: Shore A hardness values increased from a low of 9.4 (+/- 0.5) units immediately after fabrication to a maximum of 15.9 (+/- 1.1) units after 1 year. Mode of polymerization did not influence hardness (p = .9851). Water-sorption values ranged from 4.2 (+/- 0.2%) of dry weight to 14.7 (+/- 2.5%) after 1 year. Resin solubility varied from 10.3 (+/- 0.6%) of preimmersion weight to 15.4 (+/- 1.1%), and immersion duration had no effect on solubility. In addition, after 1 year of storage, no difference in resin solubility or water sorption was found with respect to cure mode. The glass transition temperature for chairside-polymerized samples approximated -10 degrees C, while that for labpolymerized samples approximated -15 degrees C. CONCLUSIONS: With regard to the material properties evaluated in this study, clinically processed Permasoft liner was equivalent to the laboratory-processed material.

Absorption↗

PubMed2004

Cooperativity of the beta-relaxations in aromatic polymers.

The dielectric loss spectra of a series of copolyesters of poly(ethylene terephthalate) and poly(ethylene isophthalate) have been measured as a function of temperature in a broad frequency range (10(-1)-10(9) Hz). By these measurements, the merging of the two relevant relaxations alpha and beta has been studied. The beta processes exhibit a complex temperature dependence, showing a clear Arrhenius dependence at temperatures well below the glass transition temperature, a transition zone where the characteristic relaxation time of this process nearly does not change with temperature, and an Arrhenius behavior with a higher activation energy for temperatures above the glass transition. The analysis of these results indicates that the beta relaxation in these systems presents typical characteristics of a genuine Johari-Goldstein process. This finding has been interpreted as due to the full monomer extension of the molecular motions involved in the beta relaxation in agreement with recent proposals.

Journal Article↗

PubMed1982

The polyisoprenoid chain length influences the interaction of ubiquinones with phospholipid bilayers.

The interaction between ubiquinone homologues with polyisoprenoid chain lengths varying from 3 to 10 units and dipalmitoylphosphatidylcholine bilayers has been examined by differential scanning calorimetry and wide angle X-ray diffraction analysis. Decreasing the polyisoprenoid chain lengths of ubiquinone in mixed dispersions with phospholipid in mol ratios of about 10 mol% caused a decrease in the gel-liquid crystalline phase transition temperature of the phospholipid and a broadening of the transition. Enthalpy measurements showed that most of the phospholipid (greater than 92%) was involved in the transition endotherm and the formation of a gel phase was also confirmed by the presence of a sharp X-ray reflection of 0.42 nm. These results are consistent with a model in which all of the ubiquinone homologous ultimately undergo a phase separation from phospholipid molecules entering a gel phase on cooling below the phase transition temperature. Reducing the length of the polyisoprenoid chain alters the amphipathic balance of the ubiquinone molecules and is reflected in the tendency of shorter chain ubiquinones to intercalate between the phospholipid molecules upon reheating through the main phase transition.

Calorimetry, Differential Scanning↗

PubMed2003

Separation of liquid phases in giant vesicles of ternary mixtures of phospholipids and cholesterol.

We use fluorescence microscopy to directly observe liquid phases in giant unilamellar vesicles. We find that a long list of ternary mixtures of high melting temperature (saturated) lipids, low melting temperature (usually unsaturated) lipids, and cholesterol produce liquid domains. For one model mixture in particular, DPPC/DOPC/Chol, we have mapped phase boundaries for the full ternary system. For this mixture we observe two coexisting liquid phases over a wide range of lipid composition and temperature, with one phase rich in the unsaturated lipid and the other rich in the saturated lipid and cholesterol. We find a simple relationship between chain melting temperature and miscibility transition temperature that holds for both phosphatidylcholine and sphingomyelin lipids. We experimentally cross miscibility boundaries both by changing temperature and by the depletion of cholesterol with beta-cyclodextrin. Liquid domains in vesicles exhibit interesting behavior: they collide and coalesce, can finger into stripes, and can bulge out of the vesicle. To date, we have not observed macroscopic separation of liquid phases in only binary lipid mixtures.

1,2-Dipalmitoylphosphatidylcholine↗

PubMed1994

Regulation by gangliosides and sulfatides of phospholipase A2 activity against dipalmitoyl- and dilauroylphosphatidylcholine in small unilamellar bilayer vesicles and mixed monolayers.

The modulation by gangliosides GM1 and GD1a, and sulfatide (Sulf) of the activity of porcine pancreatic phospholipase A2 was studied with small unilamellar vesicles of dipalmitoylphosphatidylcholine (L-dpPC) and lipid monolayers of dilauroylphosphatidylcholine (L-dlPC). The presence of Sulf always led to an increase of the maximum rate of the enzymatic reaction, irrespective on whether the vesicles were above, in the range of, or below the bilayer transition temperature. Sulf did not modify the latency period for the reaction that is observed at the bilayer transition temperature. Gangliosides inhibited the maximum rate of enzymatic activity bilayer vesicles in the gel phase but the effect was complex. When the reaction was carried out at a temperature within the range of the bilayer phase transition, the gangliosides inhibited the maximal rate of the reaction in proportion to their content in the bilayer. However, at the same time the latency period observed with vesicles of pure phospholipid at this temperature was shortened in proportion to the mole fraction of gangliosides in the bilayer. At temperatures above the bilayer phase transition, gangliosides stimulated the activity of PLA2. Preincubation of the enzyme with Sulf or gangliosides did not affect the activity against bilayer vesicles of pure substrate. These glycosphingolipids did not modify the rate or extent of desorption of the enzyme from the interface, nor the pre-catalytic steps for the interfacial activation of PLA2, or the enzyme affinity for the phospholipid substrate. Also, the activity of the enzyme was not altered irreversibly by glycosphingolipids. Our results indicate that Sulf and gangliosides modulate the catalytic activity of PLA2 at the interface itself, beyond the initial steps of enzyme adsorption and activation, probably through modifications of the intermolecular organization and surface electrostatics of the phospholipid substrate.

1,2-Dipalmitoylphosphatidylcholine↗

PubMed1976

Interaction of RNA polymerase from Escherichia coli with DNA. Effect of temperature and ionic strength on selection of T7 DNA early promoters.

Factors influencing promoter site selection by Escherichia coli RNA polymerase were investigated using T7 DNA as template. The utilization of the three major early promoters A1, A2 and A3, was followed by processing the RNA transcripts with RNAase III, which generates the three corresponding initiator RNA fragments. The three promoters proved to be functionally distinct. A strong differential effect of temperature and ionic strength on promoter selection was observed. The transition temperature of promoters A1, A2 and A3 was measured directly by preincubating, at different temperatures, RNA polymerase and T7 DNA, with primer-substrate combinations which selected each site independently. The transition temperature of the three sites was markedly different. Promoter A3 was used predominantly at low temperature, whereas A1 or A2 promoters were gradually activated by increasing the temperature. The temperature response curves were strongly dependent upon the salt concentration. On the other hand, challenge experiments with rifampicin or poly (inosinic acid) showed that, once preinitiation complexes are formed by incubating RNA polymerase with DNA at 37 degrees C, the three sites A1, A2 and A3 promote chain initiation with equal efficiency and at the same rate.

Binding Sites↗

PubMed2006

The effect of chain length on the melting temperature and size of dialkyldimethylammonium bromide vesicles.

Differential scanning calorimetry (DSC) and dynamic light scattering (DLS) were used to obtain the gel to liquid-crystalline phase transition temperature (Tm) and the apparent hydrodynamic radius (Rh) of spontaneously formed cationic vesicles of dialkyldimethylammonium bromide salts (CnH2n+1)2(CH3)2N+.Br-, with varying chain lengths. The preparation of cationic vesicles from aqueous solution of these surfactants, for n=12, 14, 16 and 18 (DDAB, DTDAB, DHDAB and DODAB, respectively), requires the knowledge of the surfactant gel to liquid-crystalline phase transition temperature, or melting temperature (Tm) since below this temperature these surfactants are poorly or not soluble in water. That series of cationic surfactants has been widely investigated as vesicle-forming surfactants, although C12 and C18, DDAB and DODAB are by far the most investigated from this series. The dependence of Tm of these surfactants on the number n of carbons in the surfactant tails is reported. The Tm obtained by DSC increases non-linearly with n, and the vesicle apparent radius Rh is about the same for DHDAB and DODAB, but much smaller for DDAB.

Alkylation↗